CN113061385B - Weather-resistant high-hardness water epoxy amino baking paint and preparation method thereof - Google Patents
Weather-resistant high-hardness water epoxy amino baking paint and preparation method thereof Download PDFInfo
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- CN113061385B CN113061385B CN202110350444.8A CN202110350444A CN113061385B CN 113061385 B CN113061385 B CN 113061385B CN 202110350444 A CN202110350444 A CN 202110350444A CN 113061385 B CN113061385 B CN 113061385B
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000003973 paint Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 30
- 239000004793 Polystyrene Substances 0.000 claims abstract description 66
- 239000003822 epoxy resin Substances 0.000 claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 61
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 34
- 239000000839 emulsion Substances 0.000 claims abstract description 33
- 229920002223 polystyrene Polymers 0.000 claims abstract description 32
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 29
- 239000004005 microsphere Substances 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 229920003180 amino resin Polymers 0.000 claims abstract description 12
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 11
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 10
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002966 varnish Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 2
- QWYXNPUTSOVWEA-UHFFFAOYSA-N 2-octylphenol;sodium Chemical compound [Na].CCCCCCCCC1=CC=CC=C1O QWYXNPUTSOVWEA-UHFFFAOYSA-N 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000002612 dispersion medium Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 5
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000005028 tinplate Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920006334 epoxy coating Polymers 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical group C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polyoxyethylene octylphenol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
Abstract
The invention discloses a weather-resistant high-hardness water-based epoxy amino baking paint and a preparation method thereof, wherein epoxy resin E-44 and N, N-methylene bisacrylamide are heated, stirred and reacted uniformly, and then hydroxyethyl acrylate and an initiator are slowly added to prepare a water-based epoxy emulsifier. Polyvinyl alcohol is used as a dispersion medium, free radical polymerization is carried out on styrene in the polyvinyl alcohol to prepare polystyrene microspheres, acrylic acid is added to serve as a chain terminator, the chain terminator reacts with ethylene glycol diglycidyl ether to improve the compatibility with aqueous epoxy resin emulsion, N-dimethyl-p-phenylenediamine is introduced to serve as a capping reagent and improve the water dispersibility of the N, N-dimethyl-p-phenylenediamine, and finally the novel aqueous epoxy reinforcing agent PS/ADGDE/DMPD is prepared. The waterborne epoxy emulsifier, the epoxy resin E44, the reinforcing agent, the surfactant, the deionized water, the amino resin and the defoaming agent are used for preparing the high-hardness and weather-resistant waterborne epoxy amino baking paint.
Description
Technical Field
The invention relates to the field of waterborne epoxy baking paint, in particular to weather-resistant high-hardness waterborne epoxy amino baking paint and a preparation method thereof.
Background
The epoxy resin is an important thermosetting resin, has the advantages of excellent adhesive property, wear resistance, high temperature resistance, chemical stability and the like, and is widely applied to the fields of adhesives, electronic instruments, buildings, machinery, coatings, advanced composite materials and the like. The E-44 type epoxy resin has the following advantages: the corrosion resistance of chemicals is good; the adhesive force is excellent; the paint film has small shrinkage, high strength and good wear resistance; the epoxy resin composition has good water resistance and can resist boiling water without falling off, but the epoxy resin composition is not soluble in water, so that the common E-44 type epoxy resin is solvent type. In recent years, however, regulations for controlling volatile organic compounds (voc) have been successively issued in many countries, so that the development of aqueous epoxy coatings has become a hot spot of interest.
The research on the water-based epoxy coating is started from 60 years in the last century abroad, and the development is already long until now, and the products are serialized. With the continuous and deep research on the water-based epoxy coating, the product is greatly improved, so that the application range of the product is wider, and the product can be used as a food can, a water storage tank and a cabin inner wall coating to a high-performance environment-adaptive terrace coating, an anticorrosive coating for steel and ships and the like. Although some domestic companies are sold, the price is high, the market demand can not be met, the solvent type epoxy resin is widely used in the fields of coatings, adhesives and the like at present, the traditional solvent type epoxy resin is developed into series of water-based epoxy resins of different varieties, the demands of various fields on water-based epoxy resins are met, and the water-based epoxy resin has wide market prospect.
Disclosure of Invention
In order to prepare the weather-resistant high-hardness water-based epoxy amino baking paint, double bonds are introduced through the reaction of N, N-methylene bisacrylamide and epoxy resin, hydroxyethyl acrylate is added to carry out free radical polymerization to prepare a polyhydroxyethyl acrylate-epoxy resin water-based epoxy resin emulsifier, and the polyhydroxyethyl acrylate-epoxy resin water-based epoxy resin emulsifier is mixed with epoxy resin according to a proportion to prepare water-based epoxy emulsion. In order to further improve the performance of a paint film, the modified polystyrene reinforcing agent is prepared, and the performances of chemical corrosion resistance, adhesive force, hardness and the like of the paint film can be obviously improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the weather-resistant high-hardness water-based epoxy amino baking paint comprises the following raw materials in parts by weight:
55-60 parts of water-based epoxy emulsion
40-45 parts of amino resin
0.5-2 parts of reinforcing agent
0.3 to 0.8 portion of surfactant
0.1 to 0.5 portion of defoaming agent
15-20 parts of deionized water
The amino resin is EH3870 type, is purchased from Hengyang pioneer New Polymer materials Co., Ltd, and has active hydrogen equivalent of 400-430; the defoaming agent is a BYK organic silicon defoaming agent; the surfactant is polyvinylpyrrolidone, sodium dodecyl benzene sulfonate or octyl phenol polyoxyethylene ether OP-10.
The following parts are parts by weight, and as a preferred technical scheme of the invention, the enhancer PS/ADGDE/DMPD comprises the following preparation steps:
(1) preparing polystyrene microspheres:
firstly, dissolving 1-2.5 parts of polyvinyl alcohol in 100 parts of deionized water, heating to 90-95 ℃, stirring to dissolve the polyvinyl alcohol, then cooling to 70 ℃, adding 1-3 parts of styrene and 0.1 part of initiator potassium persulfate, and fully stirring for reaction for 4-12 hours to prepare the polystyrene microsphere (PS microsphere).
(2) Preparation of PS/ADGDE:
adding 0.1-0.3 part of acrylic acid into the polystyrene microsphere suspension in the previous step for continuous reaction, stirring for 30min at 80 ℃, adding 0.1 part of hydroquinone as a chain terminator, adding 0.25-0.7 part of ethylene glycol diglycidyl ether, fully reacting for 5-8 h, and preparing ethylene glycol diglycidyl ether acrylate (PS/ADGDE) on the polystyrene microsphere.
(3) Preparation of PS/ADGDE/DMPD:
and adding 0.15-0.4 part of N, N-dimethyl-p-phenylenediamine (DMPD) serving as a terminal blocking agent into the PS/ADGDE suspension, reacting with the remaining epoxy group, and reacting at 70 ℃ for 2-4 h to prepare the PS/ADGDE/DMPD reinforcing agent.
The invention also provides a preparation method of the waterborne epoxy amino baking paint, which comprises the following steps:
(1) preparing a self-made waterborne epoxy emulsifier:
dissolving 2-5 parts of epoxy resin E-44 in a solvent, reacting 0.5-1.5 parts of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 4-8 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization, and forming the polyhydroxyethyl acrylate-epoxy resin, thereby preparing the waterborne epoxy emulsifier.
(2) Preparation of aqueous epoxy emulsion:
weighing 5-10 parts of epoxy resin E-44, uniformly mixing 1-3 parts of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 5-10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(3) Preparation of the waterborne epoxy amino baking varnish:
adding 0.5-2 parts of reinforcing agent PS/ADGDE/DMPD and 0.3-0.8 part of surfactant into 55-60 parts of aqueous epoxy emulsion, and uniformly mixing under stirring of a dispersion machine. And then adding 40-45 parts of amino resin and 15-20 parts of deionized water, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.1-0.5 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
The invention has the following remarkable advantages:
1. the epoxy baking varnish prepared by the invention is a water-based paint, has the characteristics of easy cleaning, no pollution and the like, and accords with the national green and healthy policy. The preparation process has low VOC emission, and the water-based epoxy baking paint with good performance and convenient use can be safely and effectively prepared.
2. The water-based epoxy emulsion used in the invention is a self-made emulsion, secondary amine in N, N-methylene bisacrylamide is utilized to perform ring-opening reaction with an epoxy group of epoxy resin, double bonds are introduced at the same time, and an initiator potassium persulfate and hydroxyethyl acrylate are added to perform free radical polymerization, so that the epoxy resin-polyhydroxyethyl acrylate type emulsifier is obtained, the hydroxyethyl acrylate can be used as a solvent to help dissolve the epoxy resin and has certain hydrophilicity, and the emulsifier has hydrophilicity after the epoxy resin is grafted by the free radical polymerization. The emulsifier has a structure similar to that of epoxy resin, so that the emulsifier has good compatibility with the epoxy resin and strong emulsifying capacity, and is a novel water-based epoxy emulsifier.
3. The reinforcing agent PS/ADGDE/DMPD prepared by the invention is a modified polystyrene reinforcing agent, polystyrene is used as a traditional reinforcing agent, and the corrosion prevention mechanism of the reinforcing agent is that some hole defects formed in the paint film forming process can be filled, so that the path of a corrosive medium entering a substrate is prolonged, however, the compatibility between polystyrene and epoxy resin is not high, and thus modification is carried out on the basis. The synthesized polystyrene microsphere is connected with acrylic acid, and then an ethylene glycol diglycidyl ether chain segment is used as a bridge, so that primary amine on N, N-dimethyl-p-phenylenediamine reacts with an epoxy group on diethanol diglycidyl ether, and the N, N-dimethyl-p-phenylenediamine is connected into the polystyrene microsphere, wherein the structure of the ethylene glycol diglycidyl ether is similar to that of epoxy resin, and the compatibility of polystyrene in the epoxy resin is improved. The N, N-dimethyl-p-phenylenediamine has a benzene ring structure, can be used as a hard section part and a part of an epoxy resin reinforcing agent, has the functions of preventing corrosive media in a paint film from entering the surface of a substrate and filling up some defects in the paint film, and simultaneously, amino groups which are not reacted by the N, N-dimethyl-p-phenylenediamine can participate in the crosslinking process of the water-based epoxy resin, so that the compactness of the paint film is improved, and the corrosion resistance is improved. The reinforcing agent keeps the anticorrosion effect of the polystyrene microspheres in the emulsion, improves the water dispersibility and compatibility of the polystyrene microspheres, performs performance modification on the basis, and is a novel waterborne epoxy emulsion reinforcing agent.
Drawings
FIG. 1 is an SEM image of enhancer PS/ADGDE/DMPD. As can be seen from the figure, the polystyrene microsphere has uniform particle size, and meanwhile, the protrusions caused by the modified polystyrene surface are provided with some dot blocks, which proves that the subsequent modification has successfully grafted the polystyrene microsphere and has no great influence on the appearance.
FIG. 2 Fourier transform infrared (FT-IR) spectrum of the aqueous epoxy emulsifier prepared in the present invention; in 1360cm-1The absorption peak of tertiary amine appears near the position, and 910cm-1The characteristic peak of the nearby epoxy resin is basically disappeared, which proves that the methylene bisacrylamide is reacted with the epoxy resinShould be used. 1297cm-1The nearby peak represents the appearance of alcoholic hydroxyl group, and 1760cm-1A saturated lactone stretching peak appears nearby, namely that the hydroxyethyl acrylate is connected with the epoxy resin.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example one
(1) Preparing polystyrene microspheres:
firstly, 1.5 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, the temperature is raised to 95 ℃, the polyvinyl alcohol is stirred to be dissolved, then the temperature is lowered to 70 ℃, 1.5 parts of styrene and 0.1 part of initiator potassium persulfate are added, and the polystyrene microspheres are prepared after fully stirring and reacting for 10 hours.
(2) Preparation of PS/ADGDE:
adding 0.1 part of acrylic acid into the polystyrene microsphere suspension in the previous step to participate in reaction, adding 0.1 part of hydroquinone as a chain terminator, stirring for 30min at 80 ℃, then adding 0.4 part of ethylene glycol diglycidyl ether, and fully reacting for 8h to form a PS/ADGDE part.
(3) Preparation of PS/ADGDE/DMPD:
0.2 part of N, N-dimethyl-p-phenylenediamine is added into the PS/ADGDE suspension as a terminating agent, and the PS/ADGDE/DMPD reinforcing agent is prepared after the reaction is carried out for 4 hours at the temperature of 70 ℃.
(4) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, reacting 0.5 part of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 6 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, and thus preparing the waterborne epoxy emulsifier.
(5) Preparation of aqueous epoxy emulsion:
weighing 10 parts of epoxy resin E-44, uniformly mixing 3 parts of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(6) Preparation of the waterborne epoxy amino baking varnish:
to 55 parts of an aqueous epoxy emulsion, 0.5 part of a reinforcing agent PS/ADGDE/DMPD and 0.4 part of sodium dodecylbenzenesulfonate were added, and uniformly mixed with stirring in a dispersion machine. And then adding 40 parts of amino resin and 15 parts of deionized water, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.2 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(7) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Example two
(1) Preparing polystyrene microspheres:
firstly, 2 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, the temperature is raised to 95 ℃, the polyvinyl alcohol is stirred to be dissolved, then the temperature is lowered to 70 ℃, 2 parts of styrene and 0.1 part of initiator potassium persulfate are added, and the polystyrene microsphere is prepared after full stirring reaction for 12 hours.
(2) Preparation of PS/ADGDE:
adding 0.3 part of acrylic acid into the polystyrene microsphere suspension in the previous step to participate in reaction, adding 0.1 part of hydroquinone as a chain terminator, stirring for 30min at 80 ℃, then adding 0.5 part of ethylene glycol diglycidyl ether, and fully reacting for 8h to form a PS/ADGDE part.
(3) Preparation of PS/ADGDE/DMPD:
0.2 part of N, N-dimethyl-p-phenylenediamine is added into the PS/ADGDE suspension as a terminating agent, and the PS/ADGDE/DMPD reinforcing agent is prepared after the reaction is carried out for 4 hours at the temperature of 70 ℃.
(4) Preparing a self-made waterborne epoxy emulsifier:
dissolving 4 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, reacting 1 part of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 6 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, and thus preparing the waterborne epoxy emulsifier.
(5) Preparation of aqueous epoxy emulsion:
weighing 4 parts of epoxy resin E-44, uniformly mixing 1 part of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(6) Preparation of the waterborne epoxy amino baking varnish:
to 60 parts of an aqueous epoxy emulsion, 1 part of a reinforcing agent PS/ADGDE/DMPD and 0.4 part of sodium dodecylbenzenesulfonate were added, and uniformly mixed with stirring in a dispersion machine. And then adding 40 parts of amino resin and 15 parts of deionized water, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.35 part of defoaming agent to finally prepare the waterborne epoxy amino baking paint.
(7) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
EXAMPLE III
(1) Preparing polystyrene microspheres:
firstly, 2.5 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, the temperature is raised to 95 ℃, the polyvinyl alcohol is stirred to be dissolved, then the temperature is lowered to 70 ℃, 3 parts of styrene and 0.1 part of initiator potassium persulfate are added, and the polystyrene microsphere is prepared after full stirring reaction for 12 hours.
(2) Preparation of PS/ADGDE:
adding 0.3 part of acrylic acid into the polystyrene microsphere suspension in the previous step to participate in reaction, adding 0.1 part of hydroquinone as a chain terminator, stirring for 30min at 80 ℃, then adding 0.6 part of ethylene glycol diglycidyl ether, and fully reacting for 8h to form a PS/ADGDE part.
(3) Preparation of PS/ADGDE/DMPD:
adding 4 parts of N, N-dimethyl-p-phenylenediamine serving as a terminating agent into the PS/ADGDE suspension, and reacting at 70 ℃ for 4 hours to prepare the PS/ADGDE/DMPD reinforcing agent.
(4) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, reacting 1.5 parts of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, and thus preparing the waterborne epoxy emulsifier.
(5) Preparation of aqueous epoxy emulsion:
weighing 10 parts of epoxy resin E-44, uniformly mixing 3 parts of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(6) Preparation of the waterborne epoxy amino baking varnish:
to 60 parts of an aqueous epoxy emulsion, 2 parts of a reinforcing agent PS/ADGDE/DMPD and 0.6 part of polyoxyethylene octylphenol ether-10 were added, and the mixture was uniformly mixed with stirring in a dispersion machine. And then adding 45 parts of amino resin and 20 parts of deionized water, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.3 part of defoaming agent to finally prepare the water-based epoxy amino baking paint.
(7) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Comparative example 1
(1) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, reacting 1.5 parts of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, and thus preparing the waterborne epoxy emulsifier.
(2) Preparation of aqueous epoxy emulsion:
weighing 10 parts of epoxy resin E-44, uniformly mixing 3 parts of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(3) Preparation of the waterborne epoxy amino baking varnish:
and adding 45 parts of amino resin and 20 parts of deionized water into 60 parts of the aqueous epoxy emulsion, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.3 part of defoaming agent to finally prepare the aqueous epoxy amino baking paint.
(4) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Comparative example No. two
Commercially available waterborne epoxy coatings were purchased.
Preparation of a paint film: the composite coating is uniformly coated on the polished iron plate, and the thickness is ensured to be 100 +/-5 mu m.
Comparative example No. three
(1) Preparing polystyrene microspheres:
firstly, 2.5 parts of polyvinyl alcohol is dissolved in 100 parts of deionized water, the temperature is raised to 95 ℃, the polyvinyl alcohol is stirred to be dissolved, then the temperature is lowered to 70 ℃, 3 parts of styrene and 0.1 part of initiator potassium persulfate are added, and the polystyrene microsphere is prepared after full stirring reaction for 12 hours.
(2) Preparing a self-made waterborne epoxy emulsifier:
dissolving 5 parts of epoxy resin E-44 in a solvent diethylene glycol monobutyl ether, reacting 1.5 parts of N, N-methylene bisacrylamide with the epoxy resin, adding 0.1 part of potassium persulfate initiator, slowly dropwise adding 8 parts of hydroxyethyl acrylate, heating and stirring for reaction to enable the hydroxyethyl acrylate to generate free radical polymerization to form the polyhydroxyethyl acrylate-epoxy resin, and thus preparing the waterborne epoxy emulsifier.
(3) Preparation of aqueous epoxy emulsion:
weighing 10 parts of epoxy resin E-44, uniformly mixing 3 parts of the waterborne epoxy emulsifier in a dispersion machine at the rotating speed of 2000r/min, and slowly dripping 10 parts of deionized water within 30min to prepare the waterborne epoxy emulsion.
(4) Preparation of the waterborne epoxy amino baking varnish:
adding 2 parts of reinforcing agent polystyrene microspheres and 0.6 part of octylphenol polyoxyethylene ether into 60 parts of aqueous epoxy emulsion, and uniformly mixing under stirring of a dispersion machine. And then adding 45 parts of amino resin and 20 parts of deionized water, uniformly dispersing by a dispersion machine at the rotating speed of 1500r/min, and adding 0.3 part of defoaming agent to finally prepare the water-based epoxy amino baking paint.
(5) Preparation of a paint film: the tinplate is uniformly polished by sand paper, and the composite coating is uniformly coated on an iron plate, so that the thickness is ensured to be 100 +/-5 microns.
Paint film performance test table:
the water-based epoxy amino baking paint film prepared by the self-made emulsifier and the performance of the water-based epoxy amino baking paint film can be seen from the table, the water-based epoxy amino baking paint film prepared by the self-made emulsifier and the performance of the water-based epoxy resin emulsion sold in the market are seen from the table, the performance of the water-based epoxy resin emulsion baked paint film prepared by the self-made emulsifier is better than that of the water-based epoxy resin emulsion sold in the market in chemical corrosion resistance and weather resistance, and the emulsion prepared by the emulsifier is proved to have improved crosslinking density and tighter crosslinking and be capable of blocking the contact of a corrosion medium and an iron substrate for a longer time.
And in the third comparative example, only polystyrene is added as a reinforcing agent and added into the waterborne epoxy amino baking paint, compared with the first comparative example, the performance of the paint film is improved to a certain extent, and the polystyrene is proved to play a certain anticorrosion role in the paint film.
In the second, third and fourth embodiments, the reinforcing agent used in the invention is the reinforcing agent PS/ADGDE/DMPD prepared by the invention, and it can be seen that the chemical corrosion resistance, salt mist resistance, hardness and adhesion of the second, third and fourth embodiments are all improved, and as the addition amount is continuously increased, the corrosion resistance of the second embodiment is relatively good, the addition amount is moderate, too little reinforcing agent cannot play an effective corrosion resistance role, and too much reinforcing agent is added, so that agglomeration of the reinforcing agent in a paint film crosslinking process is easily caused, and thus defects are caused to influence the paint film performance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. The weather-resistant high-hardness water-based epoxy amino baking paint is characterized by comprising the following raw materials in parts by weight:
55-60 parts of water-based epoxy emulsion
40-45 parts of amino resin
0.5-2 parts of reinforcing agent
0.3 to 0.8 portion of surfactant
0.1 to 0.5 portion of defoaming agent
15-20 parts of deionized water
The enhancer is PS/ADGDE/DMPD and is prepared by the following steps: firstly, dissolving polyvinyl alcohol in deionized water at the temperature of 90-95 ℃, cooling to 70 ℃, adding styrene and an initiator, fully stirring for reaction to prepare polystyrene microspheres, adding a small amount of acrylic acid for continuing the reaction, and finally adding hydroquinone as a chain terminator; continuously adding ethylene glycol diglycidyl ether to react with acrylic acid to prepare ethylene glycol diglycidyl ether acrylate (PS/ADGDE) on the polystyrene microspheres; finally adding N, N-dimethyl-p-phenylenediamine as a terminal capping agent to react with the rest epoxy group to obtain a reinforcing agent with a PS/ADGDE/DMPD structure;
the preparation method of the water-based epoxy emulsion comprises the following steps: dissolving epoxy resin E-44 in a solvent, adding N, N-methylene bisacrylamide to react with the epoxy resin E-44, adding hydroxyethyl acrylate after the reaction is finished, adding a small amount of initiator potassium persulfate, heating and stirring to enable the hydroxyethyl acrylate to undergo free radical polymerization to form epoxy resin-polyhydroxyethyl acrylate, namely the water-based epoxy emulsifier; and (3) mixing the waterborne epoxy emulsifier with epoxy resin E-44, and slowly dropwise adding deionized water to prepare the waterborne epoxy emulsion.
2. The waterborne epoxy amino baking varnish according to claim 1, wherein the amino resin has an active hydrogen equivalent of 400 to 430.
3. The waterborne epoxy amino baking varnish according to claim 1, wherein the defoamer is a BYK silicone defoamer.
4. The waterborne epoxy amino baking varnish according to claim 1, wherein the surfactant is polyvinylpyrrolidone, sodium dodecylbenzenesulfonate or octylphenol polyoxyethylene ether OP-10.
5. The preparation method of the water-based epoxy amino baking paint as claimed in claim 1, wherein the reinforcing agent and the surfactant are added into the water-based epoxy emulsion, and are uniformly mixed under stirring of a dispersion machine, then the amino resin and the deionized water are added, and after being uniformly dispersed by the dispersion machine at the rotating speed of 1500r/min, the defoaming agent is added, and finally the water-based epoxy amino baking paint is prepared.
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Effective date of registration: 20231129 Address after: No. 3 Shunda Road, Changtai District, Zhangzhou City, Fujian Province, 363900 Patentee after: Fujian Herun Packaging Coatings Co.,Ltd. Address before: Fuzhou University, No.2, wulongjiang North Avenue, Fuzhou University Town, Minhou County, Fuzhou City, Fujian Province Patentee before: FUZHOU University |